EP0217095A2 - Method of producing low-ohmic, transparent indium-tin oxide layers, especially for imagers - Google Patents
Method of producing low-ohmic, transparent indium-tin oxide layers, especially for imagers Download PDFInfo
- Publication number
- EP0217095A2 EP0217095A2 EP86111441A EP86111441A EP0217095A2 EP 0217095 A2 EP0217095 A2 EP 0217095A2 EP 86111441 A EP86111441 A EP 86111441A EP 86111441 A EP86111441 A EP 86111441A EP 0217095 A2 EP0217095 A2 EP 0217095A2
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- EP
- European Patent Office
- Prior art keywords
- transparency
- conductivity
- tin oxide
- carried out
- oxide layers
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 238000000034 method Methods 0.000 title claims abstract description 8
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 title claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 238000004544 sputter deposition Methods 0.000 claims abstract description 4
- 238000000137 annealing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 238000005496 tempering Methods 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940038031 nitrogen 10 % Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
Definitions
- amorphous hydrogen-containing silicon (a-Si: H) layers produced by plasma-activated gas phase precipitation are used today, and indium tin oxide (ITO) layers are used as transparent electrodes.
- a-Si: H amorphous hydrogen-containing silicon
- ITO indium tin oxide
- the tempering temperature is adapted to the manufacturing temperature of the a-Si: H layer (220 ° C.) and a temperature load that could change the properties of the layer is avoided.
- FIG. 2 shows the influence of the hydrogen content in the forming gas (nitrogen) on the change in resistance (R T - R FT ) / R T (left ordinate) and the change in transparency (100 - ⁇ T) / 100 (right ordinate).
- the layer was produced according to the parameters specified in the exemplary embodiment.
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Herstellen niederohmiger, transparenter Indium-Zonnoxid-Schichten, wie sie insbesondere als transparente Elektroden auf aus amorphem, wasserstoffhaltigem Silizium bestehenden Photoleiterschichten für Bildsensorelemente verwendet werden, durch Aufdampfen oder Aufstäuben der Ausgangsmaterialien in Form von Legierungen oder Oxiden auf die Photoleiterschicht und nachträgliches Tempern in Sauerstoffatmosphäre.The invention relates to a method for producing low-resistance, transparent indium zonoxide layers, such as are used in particular as transparent electrodes on photoconductor layers for image sensor elements consisting of amorphous, hydrogen-containing silicon, by vapor deposition or sputtering of the starting materials in the form of alloys or oxides onto the photoconductor layer and subsequent annealing in an oxygen atmosphere.
Bei der Herstellung von Photosensoren werden im wesentlichen drei Materialien zum Sensorbauelement zusammengefügt: eine Photoleiterschicht befindet sich sandwichartig zwischen zwei Elektroden, von denen mindestens eine Elektrode, nämlich die Deckelektrode, transparent ist und durch ihre Lichtdurchlässigkeit eine Aktivierung des Photoleiters ermöglicht.In the manufacture of photosensors, essentially three materials are combined to form the sensor component: a photoconductor layer is sandwiched between two electrodes, of which at least one electrode, namely the top electrode, is transparent and enables the photoconductor to be activated by its translucency.
Für Bildsensorelemente werden heute als Photoleiterschichten durch plasmaaktiverten Gasphasenniederschlag hergestellte amorphe wasserstoffhaltige Silizium (a-Si:H)-Schichten verwendet, als transparente Elektroden Indium-Zinnoxid (ITO)-Schichten.For image sensor elements, amorphous hydrogen-containing silicon (a-Si: H) layers produced by plasma-activated gas phase precipitation are used today, and indium tin oxide (ITO) layers are used as transparent electrodes.
Die Anforderungen, die an diese ITO-Schichten gestellt werden, sind: eine hohe Leitfähigkeit bei hoher Transparenz (mindestens 95 %). Weitere Einzelheiten über diese Anforderungen und über den Aufbau dieser ITO-Schichten sind einem Bericht von K. L. Chopra et. al. "Transparent Conductors - A Status Review" aus der Zeitschrift Thin Solid Films, 102, (1983) Seiten 1 bis 46 zu entnehmen.The requirements placed on these ITO layers are: high conductivity with high transparency (at least 95%). More details about this Requirements and the structure of these ITO layers are described in a report by KL Chopra et. al. "Transparent Conductors - A Status Review" from Thin Solid Films, 102, (1983)
Für die Herstellung der ITO-Schichten auf Photoleitern aus a-Si:H gibt es mehrere Möglichkeiten. So sind zum Beispiel nach einem Aufsatz von Habermeier aus Thin Solid Films 80 (1981), auf den Seiten 157 bis 160 oder aus einem Aufsatz von P. Nath et. al. aus Thin Solid Films 69 (1980), Seiten 63 bis 68, reaktive Aufdampfverfahren für ITO-Schichten zu entnehmen, bei denen die Legierung aus widerstandsbeheizten Wolfram- oder Wolfram/Tantal-Booten bei 420°C bzw. 350°C Substrattemperatur aufgedampft wird. Die Transparenz dieser Schichten liegt zwischen 90 bis 96 %, der gemessene Widerstand bei 20 bis 25 Ohm/□.There are several options for producing ITO layers on a-Si: H photoconductors. For example, according to an article by Habermeier from Thin Solid Films 80 (1981), on pages 157 to 160 or from an article by P. Nath et. al. from Thin Solid Films 69 (1980), pages 63 to 68, reactive vapor deposition processes for ITO layers can be found, in which the alloy from resistance-heated tungsten or tungsten / tantalum boats is vapor-deposited at a substrate temperature of 420 ° C. or 350 ° C. The transparency of these layers is between 90 to 96%, the measured resistance is 20 to 25 Ohm / □.
Aus einem Aufsatz von K. Sreenivas et. al. aus dem J. Appl. Phys. 57 (2) 15.1.1985, Seiten 384 bis 392 ist bekannt, ITO-Schichten durch HF-Zerstäuben (rf sputtering) der Legierung in Argon/Sauerstoff-Atmosphäre herzustellen und anschließend eine Temperung in Ammoniak bei 350°C durchzuführen. Durch diese Maßnahmen werden Widerstandswerte von 300 Ohm/□ - das sind 5 × 10⁻⁴ Ohm cm - (800 Å Schichtdicke) bei einer Transparenz von 95 % erhalten.From an article by K. Sreenivas et. al. from J. Appl. Phys. 57 (2) 1/15/1985, pages 384 to 392, it is known to produce ITO layers by HF sputtering of the alloy in an argon / oxygen atmosphere and then to carry out a tempering in ammonia at 350 ° C. Through these measures, resistance values of 300 Ohm / □ - that is 5 × 10⁻⁴ Ohm cm - (800 Å layer thickness) with a transparency of 95% are obtained.
Der Erfindung liegt nun die Aufgabe zugrunde, ein Verfahren anzugeben, welches die Widerstandswerte bei gleichbleibender Transparenz noch verbessert. Dabei wurde von der Erkenntnis ausgegangen, daß es durch die bei der Herstellung und durch die zur Erzielung der erforderlichen Leitfähigkeit und Transparenz nach der Herstellung erfolgte Temperaturbelastung von über 300°C zu erheblichen Beeinträchtigungen der Materialeigenschaften des aus a-Si:H bestehenden Photoleiters kommt.The invention is based on the object of specifying a method which improves the resistance values while maintaining transparency. It was based on the knowledge that the temperature load of more than 300 ° C. during production and the achievement of the required conductivity and transparency after production leads to considerable impairments of the material properties of the photoconductor consisting of a-Si: H.
Die Erfindung löst die gestellte Aufgabe bei einem Verfahren der eingangs genannten Art dadurch, daß die Temperung in zwei Schritten bei Temperaturen von maximal 200°C durchgeführt wird, wobei
- a) im ersten Schritt zur Erreichung der Transparenz in Sauerstoffatmosphäre und
- b) im zweiten Schritt für die Leitfähigkeit der Schicht in einer plasmaaktivierten Formiergasatmosphäre getempert wird.
- a) in the first step to achieve transparency in an oxygen atmosphere and
- b) in the second step for the conductivity of the layer in a plasma-activated forming gas atmosphere.
Auf diese Weise wird die Tempertemperatur an die Herstelltemperatur der a-Si:H-Schicht (220°C) angepaßt und eine Temperaturbelastung, die die Eigenschaften der Schicht verändern könnte, vermieden.In this way, the tempering temperature is adapted to the manufacturing temperature of the a-Si: H layer (220 ° C.) and a temperature load that could change the properties of the layer is avoided.
Weitere Ausgestaltungen der Erfindung ergeben sich aus den Unteransprüchen.Further refinements of the invention result from the subclaims.
Die Erfindung wird nachfolgend anhand eines Ausführungsbeispieles und der Figuren 1 und 2, welche die erzielten Ergebnisse in bezug auf Transparenz und Leitfähigkeit der Schicht zeigen, noch näher erläutert.The invention is explained in more detail below on the basis of an exemplary embodiment and FIGS. 1 and 2, which show the results obtained with regard to the transparency and conductivity of the layer.
Die Prozeßparameter für die Herstellung der erfindungsgemäßen ITO-Schicht sind folgende:
- 1. Aufdampfen des in einer Indium-Zinn (20 %)-Legierung vorliegenden Ausgangsmaterials mittels einer Elektronenstrahlkanone bei 6 kV und einem Sauerstoff-Partialdruck von 3,5 × 10⁻⁴ mbar; Aufdampfrate: 0,1 nm/sec.
- 2. Transparenztemperung in Sauerstoff-Atmosphäre, 200°C, ca. 60 Minuten lang.
- 3. Leitfähigkeitstemperung im Stickstoff-10 % Wasser stoff-Plasma mit 40 Watt HF-Leistung bei einem Druck von 1,2 mbar und einer Gasströmung von 50 sccm (Standard ccm) bei 200°C, 30 Minuten lang.
- 1. Evaporation of the starting material present in an indium tin (20%) alloy by means of an electron beam gun at 6 kV and an oxygen partial pressure of 3.5 × 10⁻⁴ mbar; Evaporation rate: 0.1 nm / sec.
- 2. Transparency tempering in an oxygen atmosphere, 200 ° C, for about 60 minutes.
- 3. Conductivity annealing in nitrogen-10% water Fabric plasma with 40 watts of HF power at a pressure of 1.2 mbar and a gas flow of 50 sccm (standard ccm) at 200 ° C for 30 minutes.
Durch den zweistufigen Temperprozeß bei einer Temperatur, die nicht höher liegt als die Temperatur, bei der die a-Si:H-Photoleiterschicht hergestellt wurde, wird eine Verbesserung der Leitfähigkeit bei gleichbleibender Transparenz der ITO-Schicht um den Faktor 7 erreicht.The two-stage annealing process at a temperature which is not higher than the temperature at which the a-Si: H photoconductor layer was produced improves the conductivity by a factor of 7 while the transparency of the ITO layer remains the same.
Die Figur 1 zeigt in einem Kurvendiagramm die Erniedrigung des Widerstandes (RT - RFT)/RT nach der plasmaaktivierten Formiergastemperung in Abhängigkeit von der Zeit t (min). RT bedeutet Widerstandsmessung nach Sauerstoff-Temperung, RFT ist die Widerstandsmessung nach der plasmaaktivierten Stickstoff-Wasserstoff-Temperung.FIG. 1 shows in a curve diagram the reduction in the resistance (R T - R FT ) / R T after the plasma-activated forming gas heating as a function of the time t (min). R T means resistance measurement after oxygen annealing, R FT is the resistance measurement after plasma activated nitrogen-hydrogen annealing.
In Figur 2 ist der Einfluß des Wasserstoffgehaltes im Formiergas (Stickstoff) auf die Widerstandsänderung (RT - RFT)/ RT (linke Ordinate) und der Transparenzänderung (100 - ΔT)/100 (rechte Ordinate) dargestellt. Die Schicht wurde hergestellt nach den beim Ausführungsbeispiel angegebenen Parametern.FIG. 2 shows the influence of the hydrogen content in the forming gas (nitrogen) on the change in resistance (R T - R FT ) / R T (left ordinate) and the change in transparency (100 - ΔT) / 100 (right ordinate). The layer was produced according to the parameters specified in the exemplary embodiment.
Wie aus dem Kurvendiagramm der Figur 2 zu entnehmen ist, liegen die optimalen Transparenz- und Widerstandswerte bei einem Wasserstoffanteil von 10 %.As can be seen from the curve diagram in FIG. 2, the optimal transparency and resistance values are at a hydrogen content of 10%.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3531473 | 1985-09-03 | ||
| DE3531473 | 1985-09-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0217095A2 true EP0217095A2 (en) | 1987-04-08 |
| EP0217095A3 EP0217095A3 (en) | 1989-03-29 |
Family
ID=6280050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86111441A Ceased EP0217095A3 (en) | 1985-09-03 | 1986-08-19 | Method of producing low-ohmic, transparent indium-tin oxide layers, especially for imagers |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0217095A3 (en) |
| JP (1) | JPS6255811A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4842705A (en) * | 1987-06-04 | 1989-06-27 | Siemens Aktiengesellschaft | Method for manufacturing transparent conductive indium-tin oxide layers |
| EP0357289A2 (en) * | 1988-08-29 | 1990-03-07 | Minnesota Mining And Manufacturing Company | Electrically conductive metal oxide coatings |
| WO1998029902A1 (en) * | 1996-12-27 | 1998-07-09 | Radiant Technologies, Inc. | Method for restoring the resistance of indium oxide semiconductors after heating while in sealed structures |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6140735A (en) * | 1984-07-31 | 1986-02-27 | ヴイエナ・ソ−セ−ジ・マニユフアクチユアリング・カンパニ− | Pastry wrapping sausage and its production |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2443746A1 (en) * | 1978-12-08 | 1980-07-04 | Exxon Research Engineering Co | Photocell, esp. solar cell giving efficient conversion - has transparent oxide electrode with low work function and selenium layer bonded by tellurium film (NL 10.6.80) |
| JPS60141862A (en) * | 1983-12-29 | 1985-07-26 | Fujitsu Ltd | Manufacture of electrically conductive transparent film |
-
1986
- 1986-08-19 EP EP86111441A patent/EP0217095A3/en not_active Ceased
- 1986-08-29 JP JP61203562A patent/JPS6255811A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2443746A1 (en) * | 1978-12-08 | 1980-07-04 | Exxon Research Engineering Co | Photocell, esp. solar cell giving efficient conversion - has transparent oxide electrode with low work function and selenium layer bonded by tellurium film (NL 10.6.80) |
| JPS60141862A (en) * | 1983-12-29 | 1985-07-26 | Fujitsu Ltd | Manufacture of electrically conductive transparent film |
Non-Patent Citations (3)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN, Band 9, Nr. 306 (C-317)[2029], 3. Dezember 1985; & JP-A-60 141 862 (FUJITSU K.K.) 26-07-1985 * |
| SOLAR CELLS, Band 13, Nr. 3, Januar 1985, Seiten 265-269, Elsevier Sequoia, Lausanne, CH; A. MADAN et al.: "New type of contact coating for amorphous silicon solar cells" * |
| THIN SOLID FILMS, Band 102, Nr. 1, April 1983, Elsevier Sequoia, Lausanne, CH; K.L. CHOPRA et al.: "Transparent conductors - a status review" * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4842705A (en) * | 1987-06-04 | 1989-06-27 | Siemens Aktiengesellschaft | Method for manufacturing transparent conductive indium-tin oxide layers |
| EP0357289A2 (en) * | 1988-08-29 | 1990-03-07 | Minnesota Mining And Manufacturing Company | Electrically conductive metal oxide coatings |
| EP0357289A3 (en) * | 1988-08-29 | 1990-10-31 | Minnesota Mining And Manufacturing Company | Electrically conductive metal oxide coatings |
| WO1998029902A1 (en) * | 1996-12-27 | 1998-07-09 | Radiant Technologies, Inc. | Method for restoring the resistance of indium oxide semiconductors after heating while in sealed structures |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0217095A3 (en) | 1989-03-29 |
| JPS6255811A (en) | 1987-03-11 |
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